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    • 专利摘要:
    The invention relates to a reactive glass with a high water resistance, which is used for an ion-selective glass electrode, it being provided that this as constituents either HfO 2 or ZrO 2 and Nb 2 O 5 or HfO 2 and Nb 2 O 5, Cs 2 O or BaO. The invention also relates to an ion-selective glass electrode and a device for measuring the ion concentration.
    公开号:CH713989A2
    申请号:CH00860/18
    申请日:2018-07-11
    公开日:2019-01-15
    发明作者:Yuji Nishio
    申请人:Horiba Advanced Techno Co Ltd；
    IPC主号:
    专利说明:

    Description: [Technical Field] The present invention relates to e.g. Reactive glass used for the pH measurement and a glass electrode.
    [Background Technology] Various properties are required of a reactive glass used for the pH measurement, e.g. a low resistance value, a small alkali error, a low expansion coefficient, having chemical resistance, water resistance, reactivity and processability.
    It is reported that, as shown in Non-Patent Literature 1, the addition of La 2 O 3 is effective to improve the water resistance of these properties.
    However, in view of the variety of the measuring objects, a reactive glass having an even higher water resistance than formerly required.
    On the other hand, the effects on the water resistance of reactive glass have hardly been examined by the addition of other metal oxides.
    [Prior art literature] [Non-patent literature] [Non-patent literature 1] "Garasu denkyokuyou garasu (glass for glass electrodes)", Shinzo OKADAetal., Kogyö kaga-ku zashi (The Journal of Chemical Industry), Voi. 61, pp. 1534-1539 (1958).
    [Overview of the Invention] [Problem to be Solved by the Invention] The present invention has been made in view of the above problems and has its main object to provide a reactive glass having a higher water resistance than conventionally, and also other properties , which are required by a reactive glass, compared to earlier not inferior.
    [Means for Solving the Problems] As a result of experiments with the addition of various metal oxides as a constituent of the reactive glass, the inventors of the present invention were able to improve the water resistance of the reactive glass by adding HfO 2 or ZrO 2 as a constituent of the reactive glass ,
    On the other hand, you found that the addition of HfO2 or ZrO2 increased the alkali error compared to earlier.
    Then, when adding Nb 2 O 5 as an alternative component of Ta 2 O 5 to H 2 O 2 or ZrO 2, they found that the other properties were not deteriorated and the alkali error could be reduced.
    That is, it is in the reactive glass of the present invention is a reactive glass, which is used for an ion-selective glass electrode, and characterized in that it contains as components HfO2 or ZrO2 and Nb2O5.
    Such a reactive glass has a higher water resistance than before and is not inferior in the other properties than the previous reactive glass.
    [0009] If it is a reactive glass containing HfO 2 or ZrO 2 in a range between 0.1 mol% and 5.0 mol% and Nb 2 O 5 in a range between 0.1 mol% and 8, 0 mol% with respect to the entire reactive glass, an improvement in the water resistance by the addition of HfO2 or ZrO2 and a reduction effect of the alkali error by the addition of Nb2O5 can be balanced.
    If it is a reactive glass, which also contains Ta2O5 as an ingredient, the chemical resistance can be further improved.
    If it is a reactive glass, which also contains Cs2O or BaO, the alkali error can be further reduced.
    When it is a reactive glass which also contains TiO 2, the viscosity of the reactive glass can be lowered, so that the processability of the reactive glass, e.g. through automation of manufacturing, can be increased.
    When it is a reactive glass which also contains Nd 2 O 3, Sc 3 O 3 or Y 2 O 3, the alkali error or the expansion coefficient can be reduced in accordance with the balance with other components, the measurement conditions, etc., and the properties of reactivity, chemical resistance or Improvement of processing can be further improved.
    Repeated studies have shown that it is a reactive glass for an ion-selective glass electrode, which is provided as well as a reactive glass containing as components HfO2 and Nb2O5, Cs2O or BaO, a high water resistance and that is not inferior in the other properties to the previous reactive glass.
    In a glass electrode equipped with the reactive glass described above, a reactive glass having a higher water resistance than before and in which, moreover, the other properties are not inferior, so that e.g. the pH of a sample having a high salt concentration, such as seawater, in which higher water resistance of the reactive glass is required as normal, can be easily measured.
    [Effects of the Invention] Since the water resistance can be improved by the reactive glass according to the present invention by the addition of HfO 2 or ZrO 2 and, in addition, the alkali defects can be reduced by the addition of Nb 2 O 5, Cs 2 O or BaO, a reactive glass can be obtained in that it has a higher water resistance than in the past and its other properties expected from a reactive glass are not inferior to earlier ones.
    [Brief Explanation of the Figures] [Fig. 1] Schematic representation of the entire apparatus for measuring the ion concentration, which is equipped with a reactive glass according to an embodiment of the present invention.
    [Embodiment of the Invention] Next, an embodiment of the present invention will be explained. A reactive glass 1 according to the present embodiment, e.g. is reactive with the pH is used for a composite glass electrode G in which an inner electrode 2 and a comparative electrode 3 are installed.
    The reactive glass 1 is, as shown in Fig. 1, used with a support tube 4 of the glass electrode G used.
    The glass electrode G is, as shown in Fig. 1, e.g. in a state of being connected to a main body 6 of an ion concentration measuring apparatus 100 through a sensor cable 5, etc.
    The main body 6 has e.g. a computing component 61, e.g. based on an output value outputted from the glass electrode G, the pH value etc. of a measurement subject calculated, and a display component 62 indicative of the measurement value of the pH value calculated by the calculation component 61, etc.
    In the following, the reactive glass 1 will be explained concretely.
    The reactive glass 1 is one having SiO 2 (50 to 70 mol%) as a main component and Li 2 O (25 to 30 mol%) as a minor component, which further contains various metal oxides.
    In the present embodiment, an example of the combination of the metal oxides which contains HfO 2 or Nb 2 O 5 and, besides that, e.g. La2O3, Ta2O5, Cs2O, BaO, TiO2, Nd2O3, Y2O3 or Sc2O3 and so on.
    When the content of HfO 3 is in a range of 0.1 mol% to 5.0 mol%, when the water resistance of the reactive glass 1 is improved by the other constituents, the alkali error in a compensatable range can be suppressed.
    Further, for the purpose of improving the alkali defect, which is increased by the addition of HfO 2, Nb 2 O 5 is added.
    The content of Nb2O5 is e.g. in a range between 0.1 mol% and 8.0 mol%. In the case of Nb 2 O 5, since the alkali error is less than that of Ta 2 O 5 conventionally added to the reactive glass 1, and the other properties are remarkably similar to those of Ta 2 O 5, the alkali error may be due to the substitution of part or all of the Ta 2 O 5 conventionally contained in the reactive glass 1 be improved by Nb2O5 without deterioration of the other properties.
    As for other ingredients, for the purpose of improving the alkali defect and the water resistance due to the results of the previous use, a content of La 2 O 3 in a range between 3.0 mol% and 8.0 mol% is preferable.
    Further, for the purpose of maintaining the chemical resistance and the water resistance, based on the results of the previous use, it is preferable that the reactive glass 1 has a content of Ta 2 O 5 in a range between 3.0 mol% and 8.0 mol%. having.
    On the other hand, if the addition of Ta 2 O 5 is too high, the workability of the reactive glass 1 decreases or devitrification of the reactive glass 1 occurs, so that the content of Ta 2 O 5 is preferably in a range between 0.01 mol% and 8.0 mol%. lies.
    In the present embodiment, moreover, Cs 2 O and BaO are added which have the effect of reducing the alkali error.
    The content of Cs 2 O is preferably in a range between 0.01 mol% and 6.0 mol%. Further, the content of BaO is preferably in a range between 0.01 mol% and 8.0 mol%.
    Further, a content of TiO 2, which reduces the expansion coefficient and improves the processability, in a range between 0.01 mol% and 8.0 mol% is preferable.
    In addition, a content of Nd 2 O 3, which reduces the alkali error and the expansion coefficient, in a range between 0.01 mol% and 3.0 mol% is preferred.
    The effect of reducing the alkali error is higher for Nd2O3 than for Nd2O5, so that by adding Nd2O3 as well, an increase in the alkali error can be more effectively suppressed by the addition of HfO2.
    Further, addition of Y 2 O 3, which improves reactivity, chemical resistance, expansion coefficient and processability, is preferable in a range between 0.01 mol% and 3.0 mol%.
    In addition, addition of Sc 2 O 3 which improves reactivity, chemical resistance (especially, hydrogen fluoride resistance), expansion coefficient, and processability is preferable in a range between 0.01 mol% and 3.0 mol%.
    The present invention is not limited to this embodiment.
    For example, in the above embodiment, HfO 2 is added, and instead of HfO 2, ZrO 2 may also be added, or both may be added.
    In the above embodiment, Cs 2 O was added to reduce the alkali error, but BaO may be added as well or both may be added.
    With the addition of both Cs2O and BaO, although the effect of reducing the alkali error increases, since the resistance value also increases, setting in the form of increasing the addition amount of Ta2O5 and Nb2O5 which has the effect of increasing the resistance value is advantageous to lower.
    It is not always necessary to add all of Ta2O5, Cs2O, BaO, TiO2, Nd2O3, Y2O3, and Sc2O3 so that addition in various combinations is possible due to the required properties and balance with other components.
    In the present embodiment, as an example of an ion-selective glass electrode G, a pH-responsive glass electrode G is indicated, but the present invention is not limited to the pH-reactive glass electrode G, but also a structure as a glass electrode G is possible using a reactive glass 1 that reacts to ions other than protons. Further, in the above embodiment, as an example, there is shown a composite glass electrode G in which a comparative electrode 3 is incorporated, but it may be a glass electrode G in which no comparative electrode 3 is incorporated.
    Incidentally, various modifications and combinations of the embodiment are possible, provided that this does not preclude the essence of the invention.
    [Examples] Hereinafter, the present invention will be concretely explained by giving examples, but the present invention is not limited to these examples.
    In these examples, each reactive glass (S1, S2, S3, S4, S5, S6 and S7) is prepared by a fusing method in which, in addition to a conventional product (R1), based on the composition of the conventional product of the group IV or IV belonging polyvalent metal elements and metallic oxides are added by the addition of an improvement in the properties of the reactive glass is expected.
    The composition of the prepared respective reactive glass is shown in the following Table 1.
    In the respective reactive glass, all elements are added, which are not marked in Table 1 with the sign "-», and in elements with a common column of the additional amount, the total additional amount of these elements is specified in the column of the additional amount ,
    Further, the total addition amount of the columns marked "*" or "" "in Table 1 is 4.00 (mol%).
    [Table 1]
    The respective reactive glass was examined for the properties of the coefficient of expansion a, the alkali error, the water resistance, the sensitivity, etc.
    First, the expansion coefficient α of the respective reactive glass brought into a bar shape of about 20 mm was measured by means of a thermal expansion meter (TDL-841, manufactured by Rigaku Corp.).
    The coefficient of expansion of the reactive glass 1 requires that the difference to the coefficient of expansion of the glass used for the support tube 4 of the glass electrode G be low.
    As the glass used for the support tube 4 of the glass electrode, one having a coefficient of expansion in a range between 90 and 100 is suitably usable, and the use of such as ± 94 is best, so that the coefficient of expansion of the one prepared here reactive glass was evaluated on the basis of this value.
    Next, to examine the sensitivity, the alkali defect and the water resistance, a film of each prepared reactive glass was formed, and each glass electrode was assembled by the use of a commercially available electrode except for the reactive glass.
    The length of the electrode portion of the thus prepared glass electrodes was 15 cm, the diameter of the reactive film 10 mm and the diameter of the support tube 12 mm.
    Double-junction sleeve Ag / AgCl electrodes were used as reference electrodes, the electrodes being connected to a desktop pH meter and the electrical potential measured.
    Regarding the water resistance, the glass electrode was evaluated by means of a T95 water reactivity immediately after immersing in an aqueous KCl solution of 3.3 mol / L for 14 days at room temperature.
    The determination of the reaction time T95 of the tap water was carried out according to British Standards (BS EN 60746). Specifically, these are:
    That is, after measuring a reference solution of pH 4, the tap water was measured for 10 minutes. The value of the electric potential of 95% of the potential difference between the measurement value of the initial reference solution of pH 4 and the measurement value of the tap water after 10 minutes was calculated, and the time from immersion in the tap water to the value of the electric potential of 95 % was determined as reaction time T95.
    The evaluation of the alkali error was carried out according to JIS standard (B 7960-1). An alkali error within 18 mV is considered as conforming to the measuring method. The alkali error can be concretely determined by the following formula (1).
    [Formula 1] Alkali error (mV) = {(9.18 / 12.9) × 59.16} - (Measured value of NaOH - measurement value of pH 9} ... (1) With respect to of the dissymmetric electrical potential, the electromotive force was entered during the respective measurement of the reference solutions of pH 4, pH 7 and pH 9.
    With respect to the sensitivity, the electromotive force of the reference solutions held at 25 ° C of pH 4, pH 7 and pH 9 was measured for 3 minutes and determined for each solution, the sensitivity to the theoretical electromotive force.
    By means of the Nernst equation, the theoretical electromotive force per 1 pH at a temperature of the solution of 25 ° C was determined as 59.16 mV. In addition, the sensitivity at the onset of the two types of reference solutions is respectively as a and b as in the following formula (2).
    [Formula 2]
    Ea and Eb in formula (1) are based on the reference electrode in each case the resulting electromotive force of the measurement solutions, where R is the gas constant 8.3145 JK_1mol_1, T is the absolute temperature (K) and F is the Faraday Constant 96485 is Cmol-1.
    With regard to the comparative precision, the reference solutions of pH 7, pH 4 and pH 9 were alternately measured 3 times and entered the difference between the largest and the smallest value of the electromotive force. The standard value of the comparative precision of the JIS standard is a maximum of 3 mV.
    With respect to the linearity, the electromotive force when immersed in the respective reference solutions of pH 4, pH 7 and pH 9 was measured and determined by the following formula (3). The default linearity of the JIS standard is ± 3 mV.
    [Formula 3] [0057]
    In this case, in formula (3), in each case A represents the electromotive force of the reference solution of pH 4, B the electromotive force of the reference solution of pH 9, and C the electromotive force of the reference solution of pH 7.
    With regard to the reactivity, the respective electrodes were immersed in the reference solutions of pH 4, pH 7 and pH 9, in NaOH of 0.1 mol% and also in HCl of 1.0 mol% , the electromotive force measured after 1 minute and after 2 minutes and recorded their difference.
    The result of a comparison of the properties of this reactive glass is shown in Table 2 below.
    [Table 2]
    In comparison, it should be noted that S1, S2, S3, SA, S5, S6 and S7, which is the experimentally prepared reactive glass, have equivalent or better properties as compared with R1 as the conventional reactive glass Sensitivity, dissymmetrical electrical potential, comparative precision, linearity, reactivity, and coefficient of expansion, and are each sufficiently useful.
    Further, even if the addition amount of e.g. of SiO 2 and the addition amount of Cs 2 O or BaO was reduced to about 4.5 mol%, a reactive glass having equivalent properties to those of S6 and S7 was produced.
    When comparing the reaction time T95 against the tap water after immersing in the aqueous KCl solution, it is noted that the water resistance of S1, S2, S4, S5, S6 and S7 is added to HfO2 or ZrO2 as compared with the conventional one reactive glass R1 is extensively improved.
    When comparing the alkali defect, it was then possible to suppress the alkali error in S3 to which Nb 2 O 5 was added in place of Ta 2 O 5, as well as conventionally or moreover.
    For S4, S5, S6 and S7 to which Nb2O5 was added in addition to Ta2O5 Nb2O5, it was found that the alkali error was suppressed to a lower value as compared with R1.
    In S1 and S2, it was found that the alkali error was somewhat larger as compared with R1, but each was an area in which they could easily be used as a reactive glass.
    In particular, in the composition of S2 without BaO in the composition of the alkali error was at least 26 mV, but by the addition of BaO, the alkali error could be suppressed to below 26 mV, so it was found that the addition of BaO the Alkaline error is reduced. With regard to the ratio of the added amounts of TiO 2 and HfO 2 or ZrO 2 shown in Table 1 as a sum, the addition amount of HfO 2 (or ZrO 2) should be e.g. at an addition amount of TiO 2 of 1.0 in a range of 3.0 to 5.0. Further, regarding the ratio of the added amounts of Nd 2 O 3 and Y 2 O 3 or Sc 2 O 3, the addition amount of Y 2 O 3 (or Sc 2 O 3) should be e.g. with an addition of Nd2O3 of 1.0 in a range between 2.0 to 3.0.
    In addition, regarding the ratio of the added amounts of Cs2O and BaO, the addition amount of BaO, e.g. with an addition amount of Cs2O of 1 in a range of 0.7 to 2.2.
    From these results, it was found that the addition of HfO 2 or ZrO 2 to the conventional composition of a reactive glass improved the water resistance on a large scale.
    In particular, when comparing the metals of group IV and group V with each other, it can be seen that the water resistance increases, the larger the atomic number is. Further, it was found that by adding Nb 2 O 5, Cs 2 O or BaO to the composition of the conventional reactive glass, the alkali error became smaller.
    In addition, it was found from the results of S1 to S7 that by the combined addition of between 0.01 mol% and 6.00 mol% of TiO2, HfO2 or ZrO2 and between 0.01 mol% and 3.00 mole% of Nb2O5 and an additional addition thereto of between 0.01 mole% to 6.40 mole% Cs2O or BaO, between 0.01 mole% and 1.50 mole% of Nd2O3, Sc2O3 or Y2O3, a reactive glass excellent in addition to the water resistance and the alkali defect can also be produced with respect to the other properties.
    In particular, it has been found that by the combined addition of HfO 2 or ZrO 2 and Nb 2 O 5 and also the addition of Cs 2 O, BaO, Nd 2 O 3, Sc 2 O 3, Y 2 O 3 etc. is a reactive glass in which the water resistance is higher and the alkali error is smaller , and also with regard to the other properties, a sufficiently useful reactive glass can be produced.
    [Explanation of Reference Numerals] [0070] 100 Ion concentration measuring device 1 Reactive glass 2 Inner electrode 3 Comparative electrode 4 Support tube 5 Sensor cable 6 Main body 61 Calculation component 62 Display component G Glass electrode
    权利要求:
    Claims (7)
    [1]
    claims
    Reactive glass used for an ion-selective glass electrode, characterized in that the reactive glass contains HfO 2 or ZrO 2 and Nb 2 O 5 or contains HfO 2 and each of Nb 2 O 5, Cs 2 O or BaO.
    [2]
    2. Reactive glass according to claim 1, characterized in that the content of HfO2 or ZrO2 in the range between 0.1 mol% and 5.0 mol% and of Nb2O5 in the range between 0.1 mol% and 8.0 Mole% with respect to the entire reactive glass.
    [3]
    3. Reactive glass according to claim 1, characterized in that it further contains Ta2O5.
    [4]
    4. Reactive glass according to claim 1, characterized in that it also contains Cs2O or BaO.
    [5]
    5. Reactive glass according to claim 1, characterized in that it further contains TiO2.
    [6]
    Reactive glass according to claim 1, characterized in that it also contains Nd 2 O 3, Sc 2 O 3 or Y 2 O 3. 7. Ion-selective glass electrode, characterized in that it comprises the reactive glass according to claim 1.
    [8]
    8. A device for measuring the ion concentration, characterized in that it comprises the ion-selective glass electrode according to claim 7.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2017138577|2017-07-14|
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